Clanis bilineata larva skin (CBLS), a new residue from the food industry, was first used to produce biochars by pyrolysis at 300 °C (CBLS300) and 700 °C (CBLS700), respectively, for Pb immobilization. The sorption isotherms and immobilization mechanisms of Pb on two biochars were investigated. CBLS700 exhibited more high-efficiency in sorption of Pb than CBLS300 due to the predicted maximum sorption capacity of CBLS700 (77.52 mg/g) was larger than that of CBLS300 (49.02 mg/g). Synchrotron-based microfocused X-ray fluorescence analysis exhibited the co-distribution of Pb and P in the sorption product of CBLS700 rather than CBLS300. Microfocused X-ray absorption near-edge structure analysis highlighted the significance of organic ligand in the biochar for Pb immobilization due to both sorption products have organic complexed Pb. Moreover, 25% of total Pb was present as hydrocerussite on CBLS300 but partially transformed into stable hydroxylpyromorphite on CBLS700 (~21%), which was in accordance with the analysis of scanning electron microscopy coupled with energy disperse spectra. Additionally, addition of CBLS700 was more effective in reducing the leachable Pb in shooting range soil than that of CBLS300. These results strongly suggested the potential application of the new biochar (CBLS700) for the remediation of Pb-contaminated soils.